Reaction products of amines with strong polybasic mineral acids



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YED STATES PA EN OFFICE nnAorlon raonnc'rs or i s rnondromnasrcivnnsmn'gicms v 1 Heinrich Ulrich, an! 7 Koerding, and Joseph?" 1 Nuesslein, Ludwigshafen-on-the-Rhine, 'Gerv many, assignorsto 1.; G. Farbenindustrie-Ab i V tiengesellschaft, Frankfort-on-the-Main, qer- 'many' y;

No Drawing. ApplicationMay 2,1931, Serial No. J, V 534,689. Renewed fNovember 5, 1934f In Gier-- many May 7, 1930*; i

:The present invention relates to the producaction and therefore correspond apparently to 11 tion of assistants for the textile and related in the general formula a a We have found that very valuable assistants @1 a p d washing, cleansing, dispersing and wetproperties andwbich arealso pable of i p p sol g watery-insoluble c mpounds such as ter insoluble alcohols,can be obtained by rel y mg o saturated or unsaturated aliphatic t in which R1 denotes an aliphatic, cycio-aliphatic 1o s; e. aliphaticopen chaimvcycloanpha'uc or aromatic radicle, R2 is the same as R1 or da h d (,"Or m e 1 hydrogen and ndenotes 1 or an integral num- -arorn ticamines, which contain at least above 15 n atoms and at least one hydroxyl group i The ph p c esters e u l y p epa edby introducing thelamines at fromsay to 85 t C; "into'a from about double to'ctrebleflquantlty t ethersofthefsaid amineawith stron of concentrated phosphoric acid orintolan equij mineral acid compound, includinganhydrides -or mole'cularqugntity Qf PhOSPhOI'uS ,oxychloride,

id w t P lli ethylene chloride for example being used as a I lorsulphonicacidioleum, suln b d I P il? ltriPXid horic acid P P P The resulting products are especially suitable ychloride, l the salqamines for washing wool and may be employed in acid,

q b i wlth ,sulphunc ester neutral or alkaline baths provided the products Phosphonc groupscontain 'morei'tha'n 8 carbon atoms; it amines y l t i, t particularly sultable for containing irom 4 to 8 carbon atoms have been it the Sam Q Q a example employed the' products are 'valuable wetting yWW1*N-hydmxyethylamine, agents for use in mercerizingliquors or other di'hydmxyemw amine alkaline-baths. Alkali met-a1 salts of the said sulllsopmfyl f i g' phuric or phosphoric estersor s'ulphonic acids g a 3 obtainable by inspissating alkaline solutions at mxye y a pressure as low as possible may be also employed for the said purposes. The products obrn-cmom-c t QTh reaction :is tcarried out for example by in-, reducing the aminesinto a double 0].;vt1f6b16 tamed may also be a in combmfllon with soaps and ;other wettmg and cleansing agents such as Turkey red oils, naphthalenesulphonlc acids; sulphot-oleic acid or sulphopalmitie acid. They are particular insensitive to hard water and prevent thezprecipitationy of" calcium soaps." it h The following examples: will furtherv illustrate the nature of this invention, but the invention is not restricted to these examples. The parts quantityofconcentrated sulphuricmaci or by tirring with chlorsulphonio, acid;.in which later case organicvinert diluents such as ethyl ether-5, ethylene gchloride or carbon tetrachloride, are preferably added. ()leum or sulphuric: ane 40 h drid mayhalsogbe employed buttinmthisgcase th reaction mixture should-be carefully cooled o us; to the strong action of the said sulphonat ga-agents; the initial reaction temperature be- I ng usually betweenfi? and;25;C., the temperaare by.weight., i t it ture be ngjth'en raised, if desired, up to say 0.; l Example 1 5 I "amines contain one 'or more double link-t t t v i ages sulphonic acids may be prepared; this reparts of N-p-ethyl hexyl-N-mono ethanolactionfbeing usuallyjcarriedgout with the a-idof amine are stirred with, or introduced into, 200

parts? of; concentrated sulphuric acid at about 50 d. Tha -sulphuric esters ob thpracticaliyneutralrechlor sulphonic aci ta ed are substances wi The reactionmixture is 305C. for '2 hours.

j stirred with 1200 parts of a mixtureof ice and) rates and is removed; whilst theaqueous soluwater, wherebythe sulphuric ester of the amine tion is neutralized with caustic alkali. The prod- 4 uct corresponds to the formula is precipitated in a. solid 'form. fAf-ter filtration it =1 may be. purified byf-crystallization from h'otj was; 1 ter; it then iormsarieutraliwhite powder readf T iiy so1ub1e5; 1ncaustic; alkalilf;ThBibrOdilCflthus;- V X obtained. ham-excellent, properti as a" Wetting ii i sg g fii gij gifiggi gifi'fiz fi i iig 5 Y agentin--mercerizingbathsz f-r,

' v y e Insteadcof'ethyl-'hekyl 'eth'anolam' eq'mva --3 P e1a,e911ne atnme t1?enmtrdued I int amounts ofN cyclohexyl N diethanolaniine a ette @Xture is 5 abwt 'N-hydroxyethyl-N tetrahydronaphthylamine or'" 44119? Wh l f the fimt w rise 26'N-cetyfN-ethainolamineniaybe,employed; .1 W abwt 1 tether 1s .dslstlued a j and 30 parts-of'ice are introduced into the rea Example 2}, "maining productfwhich is then neutralized with fi y ;fi m b y yi; caustic sodasolutio'n, The sulphonated product amine are dissolved'in wfl'parts of ethylene chlo e '25vvride. Thejsolutionobtained is poured'at about" OHwwmk-omQm-cn-(oH,)1-om-1 ;m 20?"C.into-'200-parts'of'afmixture, of equal parts...' e i t r ofzchlorosulphonic acidand ethy'lene chloride and stirred during 2 to4 hours at from 20 to C The reaction inixtureisthen pouredwinto 150 80" parts of a mixture "of ice andwater. The aquew ;,ou's.s0lutio1i ofl thegs'ulphuricester'obtained I 93.. v 1 is an-egcellent-washing agent.

" I I. Example 100 parts; of N-n-butyl-N hydroxy-isopropyl a nine are" introduced at frorn20f to,30C; into 290 parts ofyfconcentrated. sulphuric acid. The 11 I reactionproduct is then poured onto 300 parts isfsipamtdrfjriom-theylayepof ethylenechloride-v I of ice; and is rendered neutral with theaid of 1100- partsof; N-

' and-neutralizedwithcaustic'soda solution while S Q sQdaiwhile Q n s umo' u phate 4O cooling-to,.'about-E20 --.C.' wherebyfsome-commom ep rati 1 fil o e Y u 1 d n salt andGlauber's'salt are precipitated. After q g l flsolutiori of the sulphuric ester oflthe filtrationtheisolll ion d ma eminez 1 .vv .5 g' employed for increasing the' wetting powerjof oH+N1 I+-0rr on cu;)o mercerizingjliquorsn I 7 m mm e i '15?(:parts -N-cyclohexyl-N-h oxyisopropyl I 5d--iamine areintroduced at ai temperatureofi30 C. I t 1 X into 214-parts'0f,phosphoric'facid of90 percent. I v j a QT I I strength] The gmixtureji-isg heated to 501C; for ,is obtained which is practically free from sodium two. hours andthenpouredon 3o0 parts ofice. sulphate. x v I 'I'he resulting solution ;,of the; phosphoric ester, What we c1aim'is:. v v

Y- fis fi i j I L'SuIphuric estersofsecondary;amines which j i V are free from acyland-'ure'thane groups and con- 55 v tain 'analkylol Iradica'lian'd' an. aliphatici'hydro- *1 carbon radical containing at least 3 carbon atoms. 2 I Sulp tic-Lester's ofsecondary'amines'which are free' fro'macyl 'and urethane groups and con-' "'ane'tl'ian ol radica'lxand ai -aliphatic hydro- [50, 1 H' is neu'tralized witheaustic soda. n -m lice i I v played jfor'. scouring purposes. Insteadof the aIinne- 'stated,= an equimolecular quantity of N- g n-butyl-N hydroxybutyl amine prof N-hydroxyethyl-Nqauryl amine maybe-employed;-

' sulphuric esters of secondary amines. which are free from *acyl and urethane groups and .;.contain 'ain"ethano1 radical and'an aliphatic hydrocarbon radical containing from; 3 to 4 carbon atoni'sw 1 e w; H I a, "'4; As-assistants for the"textileandrelatedin- .217 parts of, themono-hydroxyethyl ether .0, ustries,"1phosphoric? estersx-ofsaaliphatic.ramines' ",70"N- -Nr d t l m ne are d s-I se ected fromfthe' groub consistingzofyprimary, solved in 500, partsof 1 carbon tetrachloride; f secondary and 'l-tertiary. amines gcontaining'i at gaseous" ulphuricanhydrideis led-intcthe solu e IGaSt/TQ CaIbQIi: atoms and at-least one of the, tio'n cooled at 20C. until '80 partsfithereof ;are' groups 'selected 'from'the'classconsisting of hy-' absorbed; '300 partsfof'ice are 'thenintroduced Qdroxyl gro'ups and-aliphalticfgroups vwith rolefinic {5 into themixture; thecarbontetrachloride sepafgj' double-linkages, whichiaminesare tfreefromacyl and urethane groups and. in which amines any organic radical attached to the nitrogen atom of said amines is an aliphatic group.

' 5., As assistants for the textile and related industries, phosphoric esters of alkylol amines selected from the group consisting of primary, secondary and tertiary amines containing at least 4 carbon atoms, which amines are free from acyl and urethane groups and in which amines any organic radical attached to the nitrogen atom of said amines is an aliphatic group.

6. Phosphoric esters of secondary amines which are free from acyl and urethane groups and contain an alkylol radical andan aliphatic hydrocarbon radical containing at least 3 carbonatoms;

7. The chemical, combination of an aminev which is free from acyl and urethane groups,

containslat least 4 carbon atoms and has attachedto the nitrogen atom thereof, an aliphatic group containing at least one of the groups selected from the class consisting of .hydroxyl groups and olefinic linkageswith a strong polybasic mineral acid.

i 8. Asassistants for the textile and related industries chemical combinations of a strong polybasicmineral acid compound with an amine corresponding to the formula wherein X stands foran aliphatic radical, Y and Z for hydrogen or an aliphatic or aromatic radical, at least one of said aliphatic radicals containing at least one of the groupings selected from the class consisting of the said amines being free from acyl and urethane groups andcontaining in the molecule at least 4 carbon atoms and, if Y and Z are y hydrogen, not more than 6 carbon atoms.

10. As assistants for the textile and related in-] sisting of OH and CH=CH,

dustries sulphonation products of an amine corresponding to the formula wherein X stands for an aliphatic radical, Y and Z for hydrogen or an aliphatic radical, at least one of said aliphatic radicals containing at least one of the groupings selected from the class conthe said amines being free from acyl and urethane groups and containing in the molecule at least 4 carbon atoms and, if Y and Z are hydrogen, not more than 6 carbon atoms.

11. As assistants for the textile and related industries sulphonation products of an amine corf responding to the formula wherein X stands for an aliphatic radical, ,Y and Z for hydrogen or an aliphatic or aromatic radical, at least one of said aliphatic radicals containing at least one of the groupings selected from the class consisting of the said amines being free from acyl and urethane groups and containing in the molecule at least 4 carbon atoms and, if Y and Z are hydrogen, not more than 6 carbon atoms.

12. As assistants for the textile and related industries sulphuric esters of an amine corresponding to the general formula wherein X is an alkylol group, Y and Z stand for hydrogenor an aliphatic radical, the said amines being free, from acyl and urethane groups and containing at least 4 carbon atoms and, if Y and Z are hydrogen, not more than 6 carbon atoms.

13. As assistants for the textile and related industries sulphuric esters of an amine which is free from acyl and urethane groups and which corresponds to the general formula wherein X is an alkylol group, Y is an aliphatic hydrocarbon radical, Z is a hydrogen or an aliphatic radical, the sum of the carbon atoms in the said amine being at least 4.

1 HEINRICH ULRICH.

PAUL KOERDING. JOSEPH NUESSLEIN. 

